Hydrochloric Acid → Cyantraniliprole

HRID 554702Notes

Reaction equation

HRID 554702 reaction equation
[Br:1][C:2]1[CH:6]=[C:5]([C:7]([OH:9])=O)[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1.[NH2:17][C:18]1[C:27]([CH3:28])=[CH:26][C:25]([C:29]#[N:30])=[CH:24][C:19]=1[C:20]([NH:22][CH3:23])=[O:21].N1C=CC=C(C)C=1.CS(Cl)(=O)=O.Cl>C(#N)C.O>[Br:1][C:2]1[CH:6]=[C:5]([C:7]([NH:17][C:18]2[C:19]([C:20]([NH:22][CH3:23])=[O:21])=[CH:24][C:25]([C:29]#[N:30])=[CH:26][C:27]=2[CH3:28])=[O:9])[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 79703-MethylpyridineHCID 31297Methanesulfonyl chlorideHCID 115875353-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acidHCID 251572822-Amino-5-cyano-N,3-dimethylbenzamide

Product 1

HCID 11578610Cyantraniliprole

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
-7.5 °C

Procedure

To a mixture of 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (see PCT Patent Publication WO 2003/015519 for a method of preparation) (97.6% purity, 3.10 g, 0.01 mol) and 2-amino-5-cyano-N,3-dimethylbenzamide (i.e. prepared by the method of Example 2) (2.00 g, 0.01 mol) in acetonitrile (24 mL) was added 3-picoline (2.92 mL, 0.03 mol). The mixture was cooled to between −5 and −10° C., and then methanesulfonyl chloride (1.08 mL, 0.014 mol) was added dropwise. The mixture was stirred for 5 minutes at −10 to −5° C., and then for 3 h at 0 to 5° C. After 3 h water (11 mL) was added dropwise to the mixture while maintaining the temperature at 0 to 5° C. After 15 minutes, concentrated hydrochloric acid (1.0 mL) was added and the mixture was stirred for 1 h at 0 to 5° C. The mixture was filtered and the solids collected were washed with acetonitrile-water (2:1 mixture, 2×2 mL) and acetonitrile (2×2 mL), and then dried under nitrogen to afford the title compound (4.78 g, 95.8% corrected yield based on assay of 95%) as an off-white solid melting at 206-208° C.

Workup

  1. temperatureThe mixture was cooled to between −5 and −10° C.
  2. waitfor 3 h at 0 to 5° C
  3. temperaturewhile maintaining the temperature at 0 to 5° C
  4. waitAfter 15 minutes
  5. stirringthe mixture was stirred for 1 h at 0 to 5° C
  6. filtrationThe mixture was filtered
  7. customthe solids collected
  8. washwere washed with acetonitrile-water (2:1 mixture, 2×2 mL) and acetonitrile (2×2 mL)
  9. customdried under nitrogen

Sources & evidence

ORD record
ord-ddd6e84fe0344676a6ff1ffb12c1f415
Source dataset
uspto-grants-2011_11
Patent number
US08049029B2

Reaction notes

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